Method for selective deposition of silicon nitride layer and structure including selectively-deposited silicon nitride layer

ABSTRACT

A method for selectively depositing silicon nitride on a first material relative to a second material is disclosed. An exemplary method includes treating the first material, and then selectively depositing a layer comprising silicon nitride on the second material relative to the first material. Exemplary methods can further include treating the deposited silicon nitride.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of U.S. Provisional Patent Application Ser. No. 62/815,820, filed Mar. 8, 2019 and entitled “METHOD FOR SELECTIVE DEPOSITION OF SILICON NITRIDE LAYER AND STRUCTURE INCLUDING SELECTIVELY-DEPOSITED SILICON NITRIDE LAYER,” which is hereby incorporated by reference.

FIELD OF INVENTION

The present disclosure generally relates to methods of forming thin films and to structures including the thin films. More particularly, the disclosure relates to methods of forming structures that include a silicon nitride layer and to structures including such layers.

BACKGROUND OF THE DISCLOSURE

Features formed using silicon nitride films are used for a wide variety of applications. For example, such features can be used as insulating regions, as etch stop regions, and for etch-resistant protective regions in the formation of electronic devices.

Typically, to form features including silicon nitride, a film of silicon nitride is deposited, the deposited film is then patterned using, for example, photolithography, and then the film is etched to formed desired features including silicon nitride material. However, as device features continue to decrease in size, it becomes increasingly difficult to pattern and etch silicon nitride films to form features of desired dimensions. Additionally, lithography and etch steps can increase costs associated with device manufacturing and increase an amount of time required for device fabrication.

Accordingly, improved methods for forming structures including silicon nitride films are desired.

SUMMARY OF THE DISCLOSURE

Various embodiments of the present disclosure relate to methods of forming features including silicon nitride and to the features including silicon nitride. While the ways in which various embodiments of the present disclosure address drawbacks of prior methods and structures are discussed in more detail below, in general, various embodiments of the disclosure provide improved methods of selectively depositing silicon nitride on one material on a substrate surface relative to another material on the substrate surface.

In accordance with at least one embodiment of the disclosure, a method of forming a structure includes providing a substrate within a reaction chamber, the substrate comprising a surface comprising a first material and a second material; treating the first material with a plasma treatment; and selectively depositing a layer comprising silicon nitride on the second material relative to the first material. The first material can include an oxide and the second material can comprise a nitride. Exemplary oxides include Group IV oxides, such as silicon oxide, and metal oxides, such as titanium oxides. By way of example, the oxide can be or include (e.g., thermally-deposited) silicon oxide. Exemplary nitrides include Group IV nitrides, such as silicon nitride, and metal nitrides, such as titanium nitrides. By way of example, the nitride can be or include silicon nitride.

The step of selectively depositing a layer comprising silicon nitride can include atomic layer deposition (ALD). Further, the step of selectively depositing a layer comprising silicon nitride can be thermal or plasma enhanced. A temperature of a susceptor within the reaction chamber and/or a reaction chamber during the step of selectively depositing is between about 100° C. and about 500° C. or between about 200° C. and about 400° C. A pressure within the reaction chamber can range from about 0.5 to about 50 or about 5 to about 15 Torr. Exemplary methods can further include a step of densifying the layer comprising silicon nitride—e.g., using a plasma treatment, wherein the plasma is formed using, for example, one or more noble gasses and helium.

In accordance with additional embodiments of the disclosure, a structure includes a feature including silicon nitride. The feature can be formed using methods as described herein. By way of particular example, a feature can include a self-aligned contact nitride layer formed using a selective deposition technique as described herein.

For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described herein above. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein, without necessarily achieving other objects or advantages as may be taught or suggested herein. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments having reference to the figures, the invention not being limited to any particular embodiment disclosed.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

A more complete understanding of exemplary embodiments of the present disclosure can be derived by referring to the detailed description and claims when considered in connection with the following illustrative figures.

FIG. 1 illustrates a method of forming a structure in accordance with at least one embodiment of the disclosure.

FIG. 2 illustrates a structure in accordance with at least one embodiment of the disclosure.

It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of illustrated embodiments of the present disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.

As used herein, the term “substrate” may refer to any underlying material or materials that may be used to form, or upon which, a device, a circuit, or a film may be formed. A substrate can include a bulk material, such as silicon (e.g., single-crystal silicon) and can include one or more layers overlying the bulk material. Further, the substrate can include various topologies, such as recesses, lines, and the like formed within or on at least a portion of a layer of the substrate.

As used herein, the term “cyclical deposition” may refer to the sequential introduction of precursors/reactants into a reaction chamber to deposit a layer over a substrate and includes processing techniques such as atomic layer deposition and cyclical chemical vapor deposition.

As used herein, the term “atomic layer deposition” (ALD) may refer to a vapor deposition process in which deposition cycles, typically a plurality of consecutive deposition cycles, are conducted in a process chamber. Generally, during each cycle, a precursor is chemisorbed to a deposition surface (e.g., a substrate surface that can include a previously deposited material from a previous ALD cycle or other material), forming about a monolayer or sub-monolayer of material that does not readily react with additional precursor (i.e., a self-limiting reaction). Thereafter, in some cases, a reactant (e.g., another precursor or reaction gas) may subsequently be introduced into the process chamber for use in converting the chemisorbed precursor to the desired material on the deposition surface. The reactant can be capable of further reaction with the precursor. Further, purging steps can also be utilized during each cycle to remove excess precursor from the process chamber and/or remove excess reactant and/or reaction byproducts from the process chamber after conversion of the chemisorbed precursor. The term atomic layer deposition, as used herein, is also meant to include processes designated by related terms, such as chemical vapor atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, or organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of precursor(s)/reactive gas(es), and purge (e.g., inert) gas(es).

As used herein, the term “cyclical chemical vapor deposition” may refer to any process wherein a substrate is sequentially exposed to two or more volatile precursors, which react and/or decompose on a substrate to produce a desired deposition.

A layer including silicon nitride (SiN) can comprise, consist essentially of, or consist of silicon nitride material. Films consisting of silicon nitride can include an acceptable amount of impurities, such as carbon, chlorine or other halogen, and/or hydrogen, that may originate from one or more precursors used to deposit the silicon nitride layers. As used herein, SiN or silicon nitride refers to a compound that includes silicon and nitrogen. SiN can be represented as SiN_(x), where x varies from, for example, about 0.5 to about 2.0, where some Si—N bonds are formed. In some cases, x may vary from about 0.9 to about 1.7, from about 1.0 to about 1.5, or from about 1.2 to about 1.4. In some embodiments, silicon nitride is formed where Si has an oxidation state of +IV and the amount of nitride in the material may vary.

Turning now to the figures, FIG. 1 illustrates a method 100 of forming a structure in accordance with at least one embodiment of the disclosure. Method 100 includes the steps of providing a substrate within a reaction chamber, the substrate comprising a surface comprising a first material and a second material (step 102), treating the first material with a plasma treatment (step 104), selectively depositing a layer comprising silicon nitride on the second material relative to the first material (step 106), and optionally densifying the layer comprising silicon nitride (step 108).

During step 102, a substrate is provided into a reaction chamber of a reactor. In accordance with examples of the disclosure, the reaction chamber can form part of an atomic layer deposition (ALD) reactor. Exemplary single wafer reactors, suitable for use with method 100, include reactors designed specifically to perform ALD processes, which are commercially available from ASM International NV (Almere, The Netherlands). Exemplary suitable batch ALD reactors are also commercially available from ASM International NV. Various steps of method 100 can be performed within a single reaction chamber or can be performed in multiple reactor chambers, such as reaction chambers of a cluster tool. Optionally, a reactor including the reaction chamber can be provided with a heater to activate the reactions by elevating the temperature of one or more of the substrate and/or the reactants/precursors.

During step 102, the substrate can be brought to a desired temperature and pressure for step 104. By way of examples, a temperature (e.g., of a substrate or a substrate support) within a reaction chamber can be between about 100° C. and about 500° C. or about 200° C. and about 400° C. A pressure within the reaction chamber can be about 0.5 to about 50 or about 5 to about 15 Torr.

As noted above, the substrate provided during step 102 includes a surface comprising a first material and a second material. The first material can include an oxide and the second material can comprise a nitride. Exemplary oxides include Group IV oxides, such as silicon oxide, and metal oxides, such as titanium oxides. By way of example, a silicon oxide can include thermally-deposited (e.g., carbon-doped) silicon oxide. Exemplary nitrides include Group IV nitrides, such as silicon nitride, and metal nitrides, such as titanium nitrides.

During step 104, the first material is exposed to a plasma treatment. The plasma treatment can create or change bonding states on the first material to inhibit deposition of silicon nitride on the first material during step 106. For example, the surface of the first material can be modified to create or increase a nucleation delay of subsequent silicon nitride deposition.

In accordance with exemplary embodiments of the disclosure, the plasma for the plasma treatment can be formed using a mixture of one or more noble gasses (e.g., argon) and a gas comprising hydrogen (e.g., H₂). A ratio of the one or more noble gasses to gas comprising hydrogen can range from, for example, about 0.1:1, about 1:0.1, 0.5:1, about 1:0.5, or about 1:1.

In some embodiments, the reaction chamber for step 104 may be configured with a capacitively coupled plasma (CCP) source, an inductively coupled plasma (ICP) source or a remote plasma (RP) source. A power used to produce the plasma can range from about 150 to about 1000 W or about 400 W to about 800 W. A time (e.g., a time of the activate plasma) for step 104 can range from about 1 millisecond to about 5 minutes or about 1 second to about 2 minutes.

When the first material includes an oxide, such as silicon oxide, it is thought that hydrogen active species created with the plasma generate a high density of —OH terminated sites on the oxide surface. The high density of —OH terminated sites, in turn, cause significant nucleation delays for subsequent exposure to silicon nitride precursors and reactants. This allows for selective deposition on other surfaces.

During step 106, a layer comprising silicon nitride is selectively deposited on the second material relative to the first material. An exemplary technique for selectively depositing silicon nitride on the first material relative to the second material includes a cyclical deposition process, such as an ALD process.

The same reaction chamber or separate reaction chambers can be utilized for steps 104 and 106. In embodiments where different reaction chambers are utilized for steps 104 and 106, the substrate may be transferred from a first reaction chamber (for treatment) to a second reaction chamber (for selective silicon nitride deposition) without exposure to the ambient atmosphere. In other words, methods of the disclosure may comprise treating the first material and selectively forming the silicon nitride film on the substrate in the same semiconductor processing apparatus. The semiconductor processing apparatus utilized for steps 104 and 106 may comprise a cluster tool which comprises two or more reaction chambers and which may further comprise a transfer chamber through which the substrate may be transported between the first reaction chamber and the second reaction chamber. In some embodiments, the environment within the transfer chamber may be controlled, i.e., the temperature, pressure and ambient gas can be controlled, such that the substrate, and particularly the cyclical silicon nitride, are not exposed to the ambient atmosphere.

One cyclic or ALD cycle may comprise exposing the substrate to a first reactant (also referred to herein as a precursor), removing any unreacted first reactant and reaction byproducts from the reaction space and exposing the substrate to a second reactant, followed by a second removal step. The first reactant may include, for example, a silicon halide or other silicon source. Exemplary silicon halides include silicon tetraiodide (SiI₄), silicon tetrabromide (SiBr₄), silicon tetrachloride (SiCl₄), hexachlorodisilane (Si₂Cl₆), hexaiododisilane (Si₂I₆), octoiodotrisilane (Si₃I₈). The second reactant may comprise a nitrogen source, such as nitrogen gas, ammonia (NH₃), hydrazine (N₂H₄) or an alkyl-hydrazine, wherein the alkyl-hydrazine may refer to a derivative of hydrazine which may comprise an alkyl functional group and may also comprise additional functional groups. Non-limiting example embodiments of an alkyl-hydrazine may comprise at least one of tertbutylhydrazine (C₄H₉N₂H₃), methylhydrazine (CH₃NHNH₂) or dimethylhydrazine ((CH₃)₂N₂NH₂).

During the purge steps, precursors/reactants can be temporally separated by inert gases, such as argon (Ar), nitrogen (N₂) or helium (He) and/or a vacuum pressure to prevent or mitigate gas-phase reactions between reactants and enable self-saturating surface reactions. In some embodiments, however, the substrate may be moved to separately contact a first vapor phase reactant and a second vapor phase reactant. Because the reactions can self-saturate, strict temperature control of the substrates and precise dosage control of the precursors may not be required. However, the substrate temperature is preferably such that an incident gas species does not condense into monolayers or multimonolayers nor thermally decompose on the surface. Surplus chemicals and reaction byproducts, if any, are removed from the substrate surface, such as by purging the reaction space or by moving the substrate, before the substrate is contacted with the next reactive chemical.

In some embodiments, exposing the substrate to a silicon halide source may comprise pulsing the silicon precursor over the substrate for a time period of between about 0.5 seconds and about 30 seconds, or between about 0.5 seconds and about 10 seconds, or between about 0.5 seconds and about 5 seconds. In addition, during the pulsing of the silicon halide source over the substrate, the flow rate of the silicon halide source may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 250 sccm or even less than 100 sccm.

In some embodiments, exposing the substrate to the nitrogen source may comprise pulsing the nitrogen source over the substrate for a time period of between about 0.5 seconds to about 30 seconds, or between about 0.5 seconds to about 10 seconds, or between about 0.5 seconds to about 5 seconds. During the pulsing of the nitrogen source over the substrate, the flow rate of the nitrogen source may be less than 4000 sccm, or less than 2000 sccm, or less than 1000 sccm, or even less than 250 sccm.

The second vapor phase reactant comprising a nitrogen source may react with silicon-containing molecules left on the substrate surface. In some embodiments, the second phase nitrogen source may react with the silicon-containing molecules left on the substrate surface to deposit a cyclical silicon nitride film.

The cyclical deposition (e.g., ALD) process for selectively depositing a layer comprising silicon nitride may be repeated (loop 116) one or more times until the desired thickness of the cyclical silicon nitride is achieved. For example, the cyclical deposition process comprises forming the cyclical silicon nitride film with a thickness of between approximately 0.3 nm and approximately 30 nm.

Once an initial desired thickness of the silicon nitride film is deposited, method 100 may proceed to step 108, densifying the layer comprising silicon nitride, in order to improve the material characteristics (e.g., a wet etch rate in, for example, hydrofluoric acid and/or phosphoric acid) of the deposited silicon nitride film. The same reaction chamber or separate reaction chambers can be utilized for deposition silicon nitride film and a step of exposing the layer comprising silicon nitride to a plasma treatment. If a separate reaction chamber, the two chambers can be part of a cluster tool as described above.

During step 108, a source gas from which the plasma is generated may comprise one or more of nitrogen (N₂), helium (He), hydrogen (H₂) and argon (Ar). In particular embodiments of the disclosure, the source gas from which the plasma is generated may comprise a mixture of helium (He) and nitrogen (N₂) and the proportion of helium (He) gas to nitrogen (N₂) gas may be equal, i.e., 50% helium gas (He) to 50% nitrogen gas (N₂) (50:50). In alternate embodiments, the proportion of helium (He) gas to nitrogen (N₂) gas may be 10%:90%, or 20%:80%, or 30%:70%, or 40%:60%, or 60%:40%, or 70%:30%, or 80%:20%, or 90%:10%, or any ranges therebetween.

In some embodiments of the disclosure, exposing the layer comprising silicon nitride to a plasma treatment may comprise applying a power to the plasma source gas (es) of between about 150 W to about 1000 W or about 400 W to about 800 W. The reaction chamber pressure can be less than 2 Torr or may even operate at a pressure of approximately 1 Torr, such as between about 0.1 Torr to about 10 Torr. In some embodiments, the substrate may be heated during the plasma treatment process to a temperature of greater than approximately 100° C., or to a temperature of greater than approximately 200° C., or even to a temperature of greater than approximately 250° C., or to a temperature between about 200° C. and about 600° C.

In some embodiments of the disclosure, exposing the silicon nitride film to a plasma comprises exposing the silicon nitride to a plasma for a time period of less than approximately 300 seconds, or for a time period of less than 150 seconds or even for a time period of less than 90 seconds. In certain embodiments of the disclosure, the silicon nitride may be exposed to the plasma treatment for a longer period of time, for example, for a time period greater than 2 minutes, or greater than 5 minutes, or even greater than 10 minutes. It should be noted that the longer silicon nitride film is exposed to the plasma, the more likely that the beneficial effects of the plasma treatment are to saturate; however, very long plasma exposure times may result in damage to the silicon nitride film.

By way of particular example, a helium (He) and nitrogen (N₂) (50%:50%) gas plasma in a reaction chamber comprising a capacitively coupled plasma (CCP) source with a plasma power of 600 W, a substrate temperature of about 200° C. to about 600° C., and a reaction chamber pressure of 2 Torr for a time period of 90 seconds can be used to treat silicon nitride.

Step 108 can be repeated (loop 110) or step 108 be performed after each silicon nitride deposition cycle or after a predetermined—e.g., two or more—deposition cycles (loop 116). The deposition cycles (step 106) and plasma treatment steps (step 108) can be repeated a desired number of times (loop 112) until a desired thickness of the silicon nitride is obtained. Additionally or alternatively, steps 104-106 or 108 can be repeated (loop 114).

FIG. 2 illustrates a structure 200 in accordance with exemplary embodiments of the disclosure. Structure 200 includes a substrate 202, a first material 204, 208, a second material 206, and selectively deposited silicon nitride 210.

Substrate 202 can include any suitable material, such as semiconductor material and materials typically used to form semiconductor devices. By way of example, substrate 202 can be or include silicon, other Group IV semiconductor material, a Group III-V semiconductor, and/or a Group II-VI semiconductor.

First material 204, 208 can include any of the first materials noted above. For example, first material 204 and/or 208 can include an oxide, such as a Group IV or metal oxide. Second material 206 can include, for example, a Group IV or metal nitride.

Silicon nitride 210 can be selectively deposited over (e.g., in direct contact with) second material 206 using a method as described herein.

The example embodiments of the disclosure described above do not limit the scope of the invention, since these embodiments are merely examples of the embodiments of the invention, which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the disclosure, in addition to those shown and described herein, such as alternative useful combinations of the elements described, may become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims. 

What is claimed is:
 1. A method of forming a structure, the method comprising the steps of: providing a substrate within a reaction chamber, the substrate comprising a surface comprising a first material and a second material, the first material comprising an oxide and the second material comprising a nitride; treating the first material with a plasma treatment to generate —OH terminals on the first material; and selectively depositing a layer comprising silicon nitride on the second material relative to the first material.
 2. The method of claim 1, wherein the step of selectively depositing comprises atomic layer deposition.
 3. The method of claim 1, wherein a temperature of a susceptor within the reaction chamber during the step of selectively depositing is between about 100° C. and about 500° C.
 4. The method of claim 1, wherein the step of treating comprises generating a plasma comprising noble gas species and hydrogen species.
 5. The method of claim 4, wherein the noble gas comprises argon.
 6. The method of claim 4, wherein a source gas for the hydrogen species comprises hydrogen.
 7. The method of claim 1, wherein a plasma for the plasma treatment is formed using a noble gas and a gas comprising hydrogen and wherein a ratio of the noble gas to gas comprising hydrogen ranges from about 0.1:1 to about 1:0.1.
 8. The method of claim 1, further comprising a step of densifying the layer comprising silicon nitride.
 9. The method of claim 8, wherein the step of densifying comprises exposing the layer comprising silicon nitride to a plasma comprising one or more noble gases.
 10. The method of claim 9, wherein the step of densifying comprises exposing the layer comprising silicon nitride to a plasma comprising helium.
 11. The method of claim 10, wherein a ratio of argon to helium is between about 0.1:0.9 and about 0.9:0.1.
 12. The method of claim 1, wherein the first material comprises an oxide selected from the group consisting of a Group IV oxide and a metal oxide.
 13. The method of claim 1, wherein the second material comprises a nitride selected from the group consisting of a Group IV nitride and a metal nitride.
 14. A method of forming a structure, the method comprising the steps of: providing a substrate within a reaction chamber, the substrate comprising a surface comprising a first material and a second material, the first material comprising an oxide and the second material comprising a nitride; treating the first material with a plasma treatment formed using a noble gas and a gas comprising hydrogen to generate —OH terminals on the first material; selectively depositing a layer comprising silicon nitride on the second material relative to the first material; and densifying the layer comprising silicon nitride.
 15. The method of claim 14, wherein the step of selectively depositing comprises atomic layer deposition. 